Crystalline transition metal molybdotungstate process data system

ABSTRACT

A hydroprocessing catalyst has been developed. The catalyst is a crystalline transition metal molybdotungstate material or metal sulfides derived therefrom, or both. The hydroprocessing using the crystalline transition metal molybdotungstate material may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking. A data system comprising at least one processor; at least one memory storing computer-executable instructions; and at least one receiver configured to receive data of a conversion process comprising at least one reaction catalyzed by the catalyst or a metal sulfide decomposition product of the catalyst has been developed.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from U.S. Provisional Application No.62/550,207 filed Aug. 25, 2017, the contents of which cited applicationare hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to a new hydroprocessing catalyst. Moreparticularly this invention relates to a crystalline transition metalmolybdotungstate and its use as a hydroprocessing catalyst.Hydroprocessing may include hydrodenitrification, hydrodesulfurization,hydrodemetallation, hydrodesilication, hydrodearomatization,hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

BACKGROUND

In order to meet the growing demand for petroleum products there isgreater utilization of sour crudes, which when combined with tighterenvironmental legislation regarding the concentration of nitrogen andsulfur within fuel, leads to accentuated refining problems. The removalof sulfur (hydrodesulfurization—HDS) and nitrogen(hydrodenitrification—HDN) containing compounds from fuel feed stocks istargeted during the hydrotreating steps of refining and is achieved bythe conversion of organic nitrogen and sulfur to ammonia and hydrogensulfide respectively.

Since the late 1940s the use of catalysts containing nickel (Ni) andmolybdenum (Mo) or tungsten (W) have demonstrated up to 80% sulfurremoval. See for example, V. N. Ipatieff, G. S. Monroe, R. E. Schaad,Division of Petroleum Chemistry, 115^(th) Meeting ACS, San Francisco,1949. For several decades now there has been an intense interestdirected towards the development of materials to catalyze the deepdesulfurization, in order to reduce the sulfur concentration to the ppmlevel. Some recent breakthroughs have focused on the development andapplication of more active and stable catalysts targeting the productionof feeds for ultra low sulfur fuels. Several studies have demonstratedimproved HDS and HDN activities through elimination of the support suchas, for example, Al₂O₃. Using bulk unsupported materials provides aroute to increase the active phase loading in the reactor as well asproviding alternative chemistry to target these catalysts.

More recent research in this area has focused on the ultra deepdesulfurization properties achieved by a Ni—Mo/W unsupported‘trimetallic’ material reported in, for example, U.S. Pat. No.6,156,695. The controlled synthesis of a broadly amorphous mixed metaloxide consisting of molybdenum, tungsten and nickel, significantlyoutperformed conventional hydrotreating catalysts. The structuralchemistry of the tri-metallic mixed metal oxide material was likened tothe hydrotalcite family of materials, referring to literature articlesdetailing the synthesis and characterization of a layered nickelmolybdate material, stating that the partial substitution of molybdenumwith tungsten leads to the production of a broadly amorphous phasewhich, upon decomposition by sulfidation, gives rise to superiorhydrotreating activities.

The chemistry of these layered hydrotalcite-like materials was firstreported by H. Pezerat, contribution a l'étude des molybdates hydratesde zinc, cobalt et nickel, C. R. ACAD. SCI., 261, 5490, who identified aseries of phases having ideal formulas MMoO₄.H₂O, EHM₂O⁻ (MoO₄)₂.H₂O,and E_(2-x)(H₃O)_(x)M₂O(MoO₄)₂ where E can be NH₄ ⁺, Na⁺ or K⁺ and M canbe Zn²⁺, Co′ or Ni′.

Pezerat assigned the different phases he observed as being Φc, Φy or Φyand determined the crystal structures for Φx and Φy, however owing to acombination of the small crystallite size, limited crystallographiccapabilities and complex nature of the material, there were doubtsraised as to the quality of the structural assessment of the materials.During the mid 1970s, Clearfield et al attempted a more detailedanalysis of the Φx and Φy phases, see examples A. Clearfield, M. J.Sims, R. Gopal, INORG. CHEM., 15, 335; A. Clearfield, R. Gopal, C. H.Saldarriaga-Molina, INORG. CHEM., 16, 628. Single crystal studies on theproduct from a hydrothermal approach allowed confirmation of the Φxstructure, however they failed in their attempts to synthesize Φy andinstead synthesized an alternative phase, Na—Cu(OH)(MoO₄), see A.Clearfield, A. Moini, P. R. Rudolf, INORG. CHEM., 24, 4606.

The structure of Φy was not confirmed until 1996 when by Ying et al.Their investigation into a room temperature chimie douce synthesistechnique in the pursuit of a layered ammonium zinc molybdate led to ametastable aluminum-substituted zincite phase, prepared by thecalcination of Zn/Al layered double hydroxide (Zn₄Al₂(OH)₁₂CO₃.zH₂O).See example D. Levin, S. L. Soled, J. Y. Ying, INORG. CHEM., 1996, 35,4191-4197. This material was reacted with a solution of ammoniumheptamolybdate at room temperature to produce a highly crystallinecompound, the structure of which could not be determined throughconventional ab-initio methods. The material was indexed, yieldingcrystallographic parameters which were the same as that of an ammoniumnickel molybdate, reported by Astier, see example M. P. Astier, G. Dji,S. Teichner, J. ANN. CHIM. (Paris), 1987, 12, 337, a material belongingto a family of ammonium-amine-nickel-molybdenum oxides closely relatedto Pezerat's materials. Astier did not publish any detailed structuraldata on this family of materials, leading to Ying et al reproducing thematerial to be analyzed by high resolution powder diffraction in orderto elucidate the structure. Ying et al named this class of materials‘layered transition-metal molybdates’ or LTMs.

SUMMARY OF THE INVENTION

A crystalline transition metal molybdotungstate material has beenproduced and optionally sulfided, to yield an active hydroprocessingcatalyst. The crystalline transition metal molybdotungstate material hasa x-ray powder diffraction pattern showing peaks at 6.2, 3.5 and 3.1 Å.The crystalline transition metal molybdotungstate material has theformula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x’ varies from 0.001 to 2, or from 0.01to 1, or from 0.1 to 0.5; ‘y’ varies from 0.4 to 3, or from 0.5 to 2 orfrom 0.6 to 1; ‘z’ is a number which satisfies the sum of the valency ofM, x and y; the material is further characterized by a x-ray powderdiffraction pattern showing peaks at the d-spacings listed in Table A:

TABLE A d(Å) I/I₀ (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

Another embodiment involves a method of making a crystalline transitionmetal molybdotungstate material having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co Ni, V, Cu, Zn, Sn, Sb, Ti,Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from 0.5to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from 0.01to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sum ofthe valency of M, x and y; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d(Å) I/I₀ (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 mwherein the method comprises: forming a reaction mixture containingwater, a source of M, a source of Mo, source of W, and optionally asolubilizing agent, complexing agent, chelating agent, or a mixturethereof; optionally removing a component from the reaction mixture togenerate an intermediate reaction mixture wherein the component is aprecipitate, or at least a portion of the water, or both a precipitateand a portion of the water; reacting the reaction mixture or theintermediate mixture at a temperature from about 25° C. to about 500° C.for a period of time from about 30 minutes to 14 days to generate thecrystalline transition metal molybdotungstate material; and recoveringthe crystalline transition metal molybdotungstate material.

Yet another embodiment involves a conversion process comprisingcontacting a sulfiding agent with a material to generate metal sulfideswhich are contacted with a feed at conversion conditions to generate atleast one product, the material comprising: a crystalline transitionmetal molybdotungstate material having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co Ni, V, Cu, Zn, Sn, Sb, Ti,Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from 0.5to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from 0.01to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sum ofthe valency of M, x and y; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

Another embodiment of the invention involves a conversion process datasystem comprising: (a) at least one processor; (b) at least one memorystoring computer-executable instructions; and (c) at least one receiverconfigured to receive data of a conversion process comprising at leastone reaction catalyzed by at least one metal sulfide resulting from thedecomposition by sulfidation of a material comprising a crystallinetransition metal molybdotungstate material having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5; ‘x’varies from 0.0001 to 0.75; ‘z’ is a number which satisfies the sum ofthe valency of M, x and y; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

The system may further comprise an Input/Output device to collect thedata, or evaluate the date, or correlate the data, or any combinationthereof. The system may further comprise a transmitter to transmit asignal to the conversion process. The signal may comprise instructions.The signal may comprise instructions regarding an adjustment to aparameter. The system may further comprise collecting data from multiplesystems wherein one system is the parameter data system. The processormay be configured to generate predictive information or quantitativeinformation.

Another embodiment of the invention is a method-of-making data systemcomprising: (a) at least one processor; (b) at least one memory storingcomputer-executable instructions; and (c) at least one receiverconfigured to receive data of a method of making a crystallinetransition metal molybdotungstate material having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof ‘x+y’ varies between 0.4 to 2.5; ‘x’ variesfrom 0.0001 to 0.75; ‘z’ is a number which satisfies the sum of thevalency of M, x and y; the material is further characterized by a x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 mwhere the method comprises (a) forming a reaction mixture containingwater, source of M, source of W, source of Mo, and optionally asolubilizing agent, complexing agent, chelating agent, or a mixturethereof; (b) optionally removing a component from the reaction mixtureto generate an intermediate reaction mixture wherein the component is aprecipitate, or at least a portion of the water, or both a precipitateand at least a portion of the water; (c) reacting the reaction mixtureor the intermediate mixture at a temperature from about 25° C. to about500° C. for a period of time from about 30 minutes to 14 days togenerate the crystalline transition metal molybdotungstate material; and(d) recovering the crystalline transition metal molybdotungstatematerial.

The system may further comprise an Input/Output device to collect thedata, or evaluate the date, or correlate the data, or any combinationthereof. The system may further comprise a transmitter to transmit asignal to the conversion process. The signal may comprise instructions.The signal may comprise instructions regarding an adjustment to aparameter. The system may further comprise collecting data from multiplesystems wherein one system is the parameter data system. The processormay be configured to generate predictive information or quantitativeinformation.

Another embodiment of the invention is a method for collecting data froma conversion process, the method comprising receiving data from at leastone sensor of a conversion process, the conversion process comprising atleast one reaction catalyzed by at least one metal sulfide derived fromthe decomposition by sulfidation of a crystalline transition metalmolybdotungstate material having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5; ‘x’varies from 0.0001 to 0.75; ‘z’ is a number which satisfies the sum ofthe valency of M, x and y; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

The conversion process may be hydroprocessing. The conversion processmay be hydrodenitrification, or hydrodesulfurization, orhydrodemetallation, or hydrodesilication, or hydrodearomatization, orhydroisomerization, or hydrotreating, or hydrofining, or hydrocracking.The method may further comprise at least one of displaying ortransmitting or analyzing the received data. The method may furthercomprise analyzing the received data to generate at least oneinstruction and transmitting the at least one instruction. The methodmay further comprise analyzing the received data and generatingpredictive information or quantitative information.

Additional features and advantages of the invention will be apparentfrom the description of the invention, figure and claims providedherein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the x-ray powder diffraction pattern of a crystallinetransition metal molybdotungstate prepared by the method as described inthe examples.

FIG. 2 illustrates a conversion process using as a catalyst, thecrystalline transition metal tungstate material, or metal sulfides asdecomposition products thereof.

FIG. 3 illustrates a method of making the crystalline transition metaltungstate material.

FIG. 4 shows a network environment and computing system that may be usedto implement embodiments of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to a conversion process data system comprising atleast one processor; at least one memory storing computer-executableinstructions; and at least one receiver configured to receive data of aconversion process comprising at least one reaction catalyzed by atleast one metal sulfide derived from a material comprising a crystallinetransition metal molybdotungstate composition. The system may furthercomprise an Input/Output device to collect the data. The system may havethe processor configured to evaluate the data. The system may have theprocessor is configured to correlate the data. The system may furthercomprise a transmitter to transmit a signal to the conversion process.The signal may comprise instructions. The signal may compriseinstructions regarding an adjustment to a parameter. The system mayfurther comprise collecting data from multiple systems wherein onesystem is the parameter data system. The processor may be configured togenerate predictive information. The processor may be configured togenerate quantitative information. The at least one unit may include,but is not limited to, reactors, distillation or fractionation units,treaters, collectors, storage vessels, strippers, utility units, and thelike.

The invention also relates to a method of making data system comprising:at least one processor; at least one memory storing computer-executableinstructions; and at least one receiver configured to receive data of aparameter of a method of making a crystalline transition metalmolybdotungstate composition where the method comprises: forming areaction mixture containing water, source of M, source of W, source ofMo, and optionally a solubilizing agent, complexing agent, chelatingagent, or a mixture thereof; optionally removing a component from thereaction mixture to generate an intermediate reaction mixture whereinthe component is a precipitate, or at least a portion of the water, orboth a precipitate and at least a portion of the water; reacting thereaction mixture or the intermediate mixture at a temperature from about25° C. to about 500° C. for a period of time from about 30 minutes to 14days to generate the crystalline transition metal tungstate material;and recovering the crystalline transition metal tungstate material.

The invention further relates to a method for collecting data from aconversion process, the method comprising receiving data from at leastone sensor of a conversion process the conversion process comprising atleast one reaction catalyzed by at least one metal sulfide derived fromthe decomposition by sulfidation of a crystalline transition metaltungstate material.

The present invention involves a crystalline transition metalmolybdotungstate composition and a process for preparing thecomposition. The material has the designation UPM-19. This compositionhas an empirical formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from0.5 to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from0.01 to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sumof the valency of M, x and y.

The crystalline composition of the invention is characterized by havingan extended network of M-O-M, where M represents a metal, or combinationof metals listed above. The structural units repeat itself into at leasttwo adjacent unit cells without termination of the bonding. Thecomposition can have a one-dimensional network, such as, for example,linear chains.

The crystalline transition metal molybdotungstate composition is furthercharacterized by a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A.

TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

The crystalline transition metal molybdotungstate composition of theinvention is yet further characterized by the x-ray powder diffractionpattern shown in the Figure.

The crystalline transition metal molybdotungstate composition can beprepared by solvothermal crystallization of a reaction mixture,typically by mixing reactive sources of molybdenum and tungsten with theappropriate source of metal ‘M’. Depending upon the metals sourcesselected, the reaction mixture may optionally include a solubilizingagent “SA” in order to facilitate the dissolution of the metals. Thereaction mixture may also optionally include a complexing agent, achelating agent, or both a complexing agent and a chelating agent “CA”in order to react with the metals prior to formation of the product.

Specific examples of suitable molybdenum sources include but are notlimited to molybdenum trioxide, ammonium dimolybdate, ammoniumthiomolybdate, and ammonium heptamolybdate. Suitable specific examplesof the tungsten source include but are not limited to tungsten trioxide,ammonium ditungstate, ammonium thiotungstate, ammonium heptatungstate,ammonium paratungstate, tungstic acid, tungsten oxytetrachloride,tungsten hexachloride, hydrogen tungstate, sodium ditungstate, sodiummetatungstate, sodium paratungstate and ammonium metatungstate. Sourcesof other metals “M” include but are not limited to the respectivehalide, acetate, nitrate, carbonate, thiols and hydroxide salts.Specific examples include nickel chloride, cobalt chloride, nickelbromide, zinc chloride, copper chloride, iron chloride, magnesiumchloride, cobalt bromide, magnesium chloride, nickel nitrate, cobaltnitrate, iron nitrate, manganese nitrate, zinc nitrate, copper nitrate,iron nitrate, nickel acetate, cobalt acetate, iron acetate, copperacetate, zinc acetate, nickel carbonate, cobalt carbonate, zinccarbonate, manganese carbonate, copper carbonate, iron carbonate, nickelhydroxide, cobalt hydroxide, manganese hydroxide, copper hydroxide, zinchydroxide, titanium oxide, manganese oxide, copper oxide, zinc oxide,cobalt oxide, nickel oxide, iron oxide, titanium tetrachloride, tinsulfate, zinc sulfate, iron sulfate, tin chloride pentahydrate, antimonychloride, antimony acetate, vanadium chloride.

Specific examples of the optional solubilizing agent “SA” include, butare not limited to, organic acids such as citric acid, malic acid,maleic acid, aliphatic acids; mineral acids such as sulfuric acid,hydrochloric acid, nitric acid, phosphoric acid and boric acid. Specificexamples of the optional complexing or chelating agents include, but arenot limited to, ammonium hydroxide, ammonium carbonate, ammoniumbicarbonate, ammonium chloride, ammonium fluoride,ethylenediaminetetraacetic acid, ethylenedimaine, methylamine,dimethylamine or a combination thereof.

Generally, the solvothermal process used to prepare the composition ofthis invention involves forming a reaction mixture wherein all of thesources of the metal components, such as for example, Ni, Mo and W aremixed together, with the optional addition of either a solubilizingagent or a complexing agent or both. The reaction may be at ambienttemperatures or at elevated temperatures. The pressure may beatmospheric pressure or autogenous pressure. The vessel used may be aclosed vessel or an open vessel. In one embodiment, the reactants arethen mixed intermittently at elevated temperatures.

By way of specific examples, a reaction mixture may be formed which interms of molar ratios of the oxides is expressed by the formula:

MO_(x):AMoO_(y):BWO_(z):C(SA):D(CA):H₂O

where ‘M’ is selected from the group consisting of iron, cobalt, nickel,manganese, vanadium, copper, zinc, tin, titanium, zirconium, antimonyand mixtures thereof; ‘x’ is a number which satisfies the valency of‘M’; ‘A’ represents the ratio of ‘Mo’ relative to ‘M’ and varies from0.0001 to 0.75, or from 0.01 to 0.6, or from 0.1 to 0.4; ‘y’ is a numbersatisfies the valency of ‘Mo’; ‘B’ represents the ratio of ‘W’ relativeto ‘M’ and varies from 0.3999 to 2.4999, or from 0.5 to 2, or from 0.7to 1.25; ‘z’ is a number satisfies the valency of ‘W’; ‘C’ representsthe ratio of the solubilizing agent (SA) relative to ‘M’ and varies from0 to 50, or from 0.1 to 25, or from 1 to 10; ‘D’ represents the ratio ofthe complexing agent (CA) relative to ‘M’ and varies from 0 to 100, orfrom 0.1 to 50, or from 5 to 20; the ratio of H₂O and varies from 0.1 to1000, or from 1 to 100, or from 2 to 20. If required, the startingreagents may be pretreat be either the addition of a complexing agentsuch as, but not limited to, ammonium hydroxide or citric acid.Depending upon the metal reagents selected, the pH of the mixture mayadjusted to an acidic or basic regime. The pH of the mixture may beadjusted through the addition of a base such as NH₄OH, quaternaryammonium hydroxides, amines, and the like, or conversely be a mineralacid such as nitric acid, hydrochloric acid, sulfuric acid hydrofluoricacid, or an organic acid such as citric acid or malic acid.

In one embodiment, an intermediate reaction mixture may be formed byremoving a component of the reaction mixture wherein the component is aprecipitate, or at least a portion of the water, or both a precipitateand at least a portion of the water mixture. The intermediate may thenreacted as the reaction mixture at a temperature from about 25° C. toabout 500° C. for a period of from about 30 minutes to 14 days togenerate the crystalline transition metal molybdotungstate compositions.

Once the reaction mixture is formed, the reaction mixture is reacted attemperatures ranging from about 25° C. to about 500° C. for a period oftime ranging from 30 minutes to around 14 days. In one embodiment, thetemperate range for the reaction is from about 300° C. to about 400° C.and in another embodiment the temperature is in the range of from about100° C. to about 200° C. In one embodiment, the reaction time is fromabout 4 to about 6 hours, and in another embodiment the reaction time isfrom about 4 to 7 days. The reaction is carried out under atmosphericpressure in an open vessel or in a sealed vessel under autogenouspressure. The crystalline transition metal molybdotungstate compositionsare recovered as the reaction product. The crystalline transition metalmolybdotungstate compositions are characterized by their x-ray powderdiffraction pattern as shown in Table A above and in the Figure.

Once formed, the crystalline transition metal molybdotungstate may havea binder incorporated, where the binder may be, for example, silicas,aluminas, silica aluminas, and mixtures thereof. The selection of binderincludes but is not limited to, anionic and cationic clays such ashydrotalcites, pyroaurite-sjogrenite-hydrotalcites, montmorillonite andrelated clays, kaolin, sepiolites, silicas, aluminas such as (pseudo)boehomite, gibbsite, flash calcined gibbsite, eta-alumina, zicronica,titania, alumina coated titania, silica-alumina, silica coated alumina,alumina coated silicas and mixtures thereof, or other materialsgenerally known as particle binders in order to maintain particleintegrity. These binders may be applied with or without peptization. Thebinder may be added to the bulk crystalline transition metalmolybdotungstate composition, and the amount of binder may range fromabout 1 to about 30 wt % of the finished catalysts or from about 5 toabout 26 wt % of the finished catalyst. The binder may be chemicallybound to the crystalline transition metal molybdotungstate composition,or may be present in a physical mixture with the crystalline transitionmetal molybdotungstate composition.

At least a portion of the crystalline transition metal molybdotungstatecomposition, with or without a binder, or before or after inclusion of abinder, can be sulfided in situ in an application or pre-sulfided toform metal sulfides which in turn are used in an application as acatalyst. The sulfidation may be conducted under a variety ofsulfidation conditions such as through contact of the crystallinetransition metal molybdotungstate composition with a sulfiding agentsuch as sulfur-containing stream or feedstream, or a gaseous mixture ofH₂S/H₂, or both. The sulfidation of the crystalline transition metalmolybdotungstate composition may be performed at elevated temperatures,typically ranging from about 50° C. to about 600° C., or from about 150°C. to about 500° C., or from about 250° C. to about 450° C. Thematerials resulting from the sulfiding step, the decomposition products,are referred to as metal sulfides which can be used as catalysts inconversion processes. As noted above, at least a portion of the metalsulfides may be present in a mixture with at least one binder. Thesulfiding step can take place at a location remote from other synthesissteps, remote from the location of the conversion process, or remotefrom both the location of synthesis and remote from location of theconversion process.

As discussed, at least a portion of the crystalline transition metalmolybdotungstate composition can be sulfided and the resulting metalsulfides may be used as a catalyst or catalyst support in conversionprocesses such as various hydrocarbon conversion processes.Hydroprocessing processes is one class of hydrocarbon conversionprocesses in which the crystalline transition metal molybdotungstatematerial is useful as a catalyst. Examples of specific hydroprocessingprocesses are well known in the art and include hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking. In one embodiment, a conversion process comprisescontacting the crystalline mixed transition metal tungstate with asulfiding agent to generate metal sulfides which are contacted with afeed stream at conversion conditions to generate at least one product.

The operating conditions of the hydroprocessing processes listed abovetypically include reaction pressures from about 2.5 MPa to about 17.2MPa, or in the range of about 5.5 to about 17.2 MPa, with reactiontemperatures in the range of about 245° C. to about 440° C., or in therange of about 285° C. to about 425° C. Time with which the feed is incontact with the active catalyst, referred to as liquid hour spacevelocities (LHSV), should be in the range of about 0.1 h⁻¹ to about 10h⁻¹, or about 2.0 h⁻¹ to about 8.0 h⁻¹. Specific subsets of these rangesmay be employed depending upon the feedstock being used. For example,when hydrotreating a typical diesel feedstock, operating conditions mayinclude from about 3.5 MPa to about 8.6 MPa, from about 315° C. to about410° C., from about 0.25/h to about 5/h, and from about 84 Nm³ H₂/m³ toabout 850 Nm³ H₂/m³ feed. Other feedstocks may include gasoline,naphtha, kerosene, gas oils, distillates, and reformate.

Any of the lines, conduits, units, devices, vessels, surroundingenvironments, zones or similar used in the process or in the method ofmaking may be equipped with one or more monitoring components includingsensors, measurement devices, data capture devices or data transmissiondevices. Signals, process or status measurements, and data frommonitoring components may be used to monitor conditions in, around, andon process equipment. Signals, measurements, and/or data generated orrecorded by monitoring components may be collected, processed, and/ortransmitted through one or more networks or connections that may beprivate or public, general or specific, direct or indirect, wired orwireless, encrypted or not encrypted, and/or combination(s) thereof; thespecification is not intended to be limiting in this respect.

Signals, measurements, and/or data generated or recorded by monitoringcomponents may be transmitted to one or more computing devices orsystems. Computing devices or systems may include at least one processorand memory storing computer-readable instructions that, when executed bythe at least one processor, cause the one or more computing devices toperform a process that may include one or more steps. For example, theone or more computing devices may be configured to receive, from one ormore monitoring component, data related to at least one piece ofequipment associated with the process. The one or more computing devicesor systems may be configured to analyze the data. Based on analyzing thedata, the one or more computing devices or systems may be configured todetermine one or more recommended adjustments to one or more parametersof one or more processes described herein. The one or more computingdevices or systems may be configured to transmit encrypted orunencrypted data that includes the one or more recommended adjustmentsto the one or more parameters of the one or more processes or methodsdescribed herein.

By way of example, sensors and measurements may be as to a parameter ofa conversion process comprising at least one reaction catalyzed by atleast one metal sulfide derived from crystalline transition metalmolybdotungstate material having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5; ‘x’varies from 0.0001 to 0.75; ‘z’ is a number which satisfies the sum ofthe valency of M, x and y; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

Such sensors or measurements may be associated with any portion orcomponent of the conversion process. Control of one or more conversionprocess parameters may be employed. The data sensed and received may beused as the basis for adjustment or control of a variety of parameterssuch as process variables and conditions. The data may providepredictive information. Similarly, sensors and measurements as to aparameter of a method of making a crystalline transition metal tungstatematerial may be associated with any portion or component of the methodof making. Control of one or more method of making parameters may beemployed. The data sensed and received may be used as the basis foradjustment or control of a variety of parameters such as processvariables and conditions. The data may provide predictive information.

FIG. 2 illustrates a conversion process where a feed in line 10 isintroduced to a reactor 30 to contact the catalyst contained withinreactor 30 and generate a reaction product. An effluent of the reactoris removed in line 40. A sulfiding agent may be included with the feedin line 10, or optionally a sulfiding agent may be introduced in line20. The catalyst contained within reactor 30 is the catalyst describedherein.

FIG. 3 illustrates a method of making the catalyst precursor materialwhere solvent and reactants in line 15 are introduced to a vessel 35 toform a reaction mixture and react within vessel 35 and generate thecrystalline transition metal tungstate material removed in line 45.Optionally, a component may be removed from the reaction mixture in line25 and introduced to second vessel 55 and reacted to form thecrystalline transition metal tungstate material in line 65.

Sensors, including analytical devices, may be employed anywherereasonable in the conversion process equipment, or method of makingequipment, as well as one or more transmitter(s), shown generally as 50.Examples of the data sensed may include process and levels monitoring,catalyst monitoring, asset health monitoring, safety applications,security monitoring and access, regulatory reporting and monitoring,asset location tracking, maintenance, turnaround activities, and thelike.

As will be appreciated by one of skill in the art upon reading thefollowing disclosure, various aspects described herein may be embodiedas a method, a computer system, or a computer program product.Accordingly, those aspects may take the form of an entirely hardwareembodiment, an entirely software embodiment or an embodiment combiningsoftware and hardware aspects. Furthermore, such aspects may take theform of a computer program product stored by one or more non-transitorycomputer-readable storage media having computer-readable program code,or instructions, embodied in or on the storage media. Any suitablecomputer-readable storage media may be utilized, including hard disks,CD-ROMs, optical storage devices, magnetic storage devices, and/or anycombination thereof. In addition, various signals representing data orevents as described herein may be transferred between a source and adestination in the form of electromagnetic waves traveling throughsignal-conducting media such as metal wires, optical fibers, and/orwireless transmission media (e.g., air and/or space).

FIG. 4 illustrates a block diagram of a sensor data analysis system ofthe parameter data system 400 that may be used according to one or moreillustrative embodiments of the disclosure. The parameter data system400 may have a processor 403 for controlling overall operation of theparameter data system 400 and its associated components, including RAM405, ROM 407, input/output module 409, and memory 415. The parameterdata system 400, along with one or more additional devices (e.g.,terminals 441, 451) may correspond to any of multiple systems ordevices, such as mobile computing devices (e.g., smartphones, smartterminals, tablets, and the like) and/or refinery-based computingdevices, configured as described herein for collecting and analyzingsensor data from devices associated with lines, vessels, or devices ofone or more units, pertaining to operation or parameter of the one ormore units.

Input/Output (I/O) 409 may include a microphone, keypad, touch screen,and/or stylus through which a user of the parameter data system 400 mayprovide input, and may also include one or more of a speaker forproviding audio output and a video display device for providing textual,audiovisual and/or graphical output. Software may be stored withinmemory 415 and/or storage to provide instructions to processor 403 forenabling parameter data system 400 to perform various functions. Forexample, memory 415 may store software used by the parameter data system400, such as an operating system 417, application programs 419, and anassociated internal database 421. Processor 403 and its associatedcomponents may allow the parameter data system 400 to execute a seriesof computer-readable instructions to transmit or receive data, analyzedata, and store analyzed data.

The parameter data system 400 may operate in a networked environmentsupporting connections to one or more remote computers, such asterminals/devices 441 and 451. Parameter data system 400, and relatedterminals/devices 441 and 451, may include devices or sensors associatedwith equipment, streams, or materials of a process employing streams anda reactor, including devices on-line or outside of equipment, streams,or materials, that are configured to receive and process data. Thus, theparameter data system 400 and terminals/devices 441 and 451 may eachinclude personal computers (e.g., laptop, desktop, or tablet computers),servers (e.g., web servers, database servers), sensors, measurementdevices, communication systems, or mobile communication devices (e.g.,mobile phones, portable computing devices, and the like), and mayinclude some or all of the elements described above with respect to theparameter data system 400.

The network connections depicted in FIG. 4 include a local area network(LAN) 425 and a wide area network (WAN) 429, and a wirelesstelecommunications network 433, but may also include other networks.When used in a LAN networking environment, the parameter data system 400may be connected to the LAN 425 through a network interface or adapter423. When used in a WAN networking environment, the parameter datasystem 400 may include a modem 427 or other means for establishingcommunications over the WAN 429, such as network 431 (e.g., theInternet). When used in a wireless telecommunications network 433, theparameter data system 400 may include one or more transceivers, digitalsignal processors, and additional circuitry and software forcommunicating with wireless computing devices 441 (e.g., mobile phones,short-range communication systems, telematics devices) via one or morenetwork devices 435 (e.g., base transceiver stations) in the wirelessnetwork 433. In one embodiment, any of the sensors and transmitters 50may communicate with receiver 435 of parameter data system 400 of FIG. 4via 77 which may be wired or wireless communication

It will be appreciated that the network connections shown areillustrative and other means of establishing a communications linkbetween the computers may be used. The existence of any of variousnetwork protocols such as TCP/IP, Ethernet, FTP, HTTP and the like, andof various wireless communication technologies such as GSM, CDMA, Wi-Fi,and WiMAX, is presumed, and the various computing devices parameter datasystem components described herein may be configured to communicateusing any of these network protocols or technologies.

Also, illustrated in FIG. 4 is a security and integration layer 460,through which communications may be sent and managed between theparameter data system 400 (e.g., a user's personal mobile device, arefinery-based system, external server, etc.) and the remote devices(441 and 451) and remote networks (425, 429, and 433). The security andintegration layer 460 may comprise one or more separate computingdevices, such as web servers, authentication servers, and/or variousnetworking components (e.g., firewalls, routers, gateways, loadbalancers, etc.), having some or all of the elements described abovewith respect to parameter data system 400. As an example, a security andintegration layer 460 of a mobile computing device, refinery-baseddevice, or a server operated by a provider, an institution, governmentalentity, or other organization, may comprise a set of web applicationservers configured to use secure protocols and to insulate the parameterdata system 400 from external devices 441 and 451. In some cases, thesecurity and integration layer 460 may correspond to a set of dedicatedhardware and/or software operating at the same physical location andunder the control of same entities as parameter data system 400. Forexample, layer 460 may correspond to one or more dedicated web serversand network hardware in an organizational datacenter or in a cloudinfrastructure supporting a cloud-based parameter data system. In otherexamples, the security and integration layer 460 may correspond toseparate hardware and software components which may be operated at aseparate physical location and/or by a separate entity.

As discussed below, the data transferred to and from various devices ofparameter data system 400 may include secure and sensitive data, such asmeasurement data, flow control data, concentration data, processparameter data, catalyst data, quantitative data, and instructions. Inat least some examples, transmission of the data may be performed basedon one or more user permissions provided. Therefore, it may be desirableto protect transmissions of such data by using secure network protocolsand encryption, and also to protect the integrity of the data whenstored in a database or other storage in a mobile device, analysisserver, or other computing devices in the parameter data system 400, byusing the security and integration layer 460 to authenticate users andrestrict access to unknown or unauthorized users. In variousimplementations, security and integration layer 460 may provide, forexample, a file-based integration scheme or a service-based integrationscheme for transmitting data between the various devices in theparameter data system 400. Data may be transmitted through the securityand integration layer 460, using various network communicationprotocols. Secure data transmission protocols and/or encryption may beused in file transfers to protect to integrity of the driving data, forexample, File Transfer Protocol (FTP), Secure File Transfer Protocol(SFTP), and/or Pretty Good Privacy (PGP) encryption.

In other examples, one or more web services may be implemented withinthe parameter data system 400 and/or the security and integration layer460. The web services may be accessed by authorized external devices andusers to support input, extraction, and manipulation of the data (e.g.,sensing data, concentration data, flow control data, etc.) between theparameter data system 400. Web services built to support the parameterdata system 400 may be cross-domain and/or cross-platform, and may bebuilt for enterprise use. Such web services may be developed inaccordance with various web service standards, such as the Web ServiceInteroperability (WS-I) guidelines. In some examples, a flow controldata and/or concentration data web service may be implemented in thesecurity and integration layer 460 using the Secure Sockets Layer (SSL)or Transport Layer Security (TLS) protocol to provide secure connectionsbetween servers (e.g., the parameter data system 400) and variousclients 441 and 451 (e.g., mobile devices, data analysis servers, etc.).SSL or TLS may use HTTP or HTTPS to provide authentication andconfidentiality.

In other examples, such web services may be implemented using theWS-Security standard, which provides for secure SOAP messages using XML,encryption. In still other examples, the security and integration layer460 may include specialized hardware for providing secure web services.For example, secure network appliances in the security and integrationlayer 460 may include built-in features such as hardware-accelerated SSLand HTTPS, WS-Security, and firewalls. Such specialized hardware may beinstalled and configured in the security and integration layer 460 infront of the web servers, so that any external devices may communicatedirectly with the specialized hardware.

In some aspects, various elements within memory 415 or other componentsin parameter data system 400, may include one or more caches, forexample, CPU caches used by the processing unit 403, page caches used bythe operating system 417, disk caches of a hard drive, and/or databasecaches used to cache content from database 421. For embodimentsincluding a CPU cache, the CPU cache may be used by one or moreprocessors in the processing unit 403 to reduce memory latency andaccess time. In such examples, a processor 403 may retrieve data from orwrite data to the CPU cache rather than reading/writing to memory 415,which may improve the speed of these operations. In some examples, adatabase cache may be created in which certain data from a database 421(e.g., an operating parameter database, a concentration database,correlation database, etc.) is cached in a separate smaller database onan application server separate from the database server. For instance,in a multi-tiered application, a database cache on an application servercan reduce data retrieval and data manipulation time by not needing tocommunicate over a network with a back-end database server. These typesof caches and others may be included in various embodiments, and mayprovide potential advantages in certain implementations of retrievingdata, collecting data, receiving data, recording data, processing data,and analyzing data, such as faster response times and less dependence onnetwork conditions when transmitting/receiving data.

It will be appreciated that the network connections shown areillustrative and other means of establishing a communications linkbetween the computers may be used. The existence of any of variousnetwork protocols such as TCP/IP, Ethernet, FTP, HTTP and the like, andof various wireless communication technologies such as GSM, CDMA, Wi-Fi,and WiMAX, is presumed, and the various computer devices and systemcomponents described herein may be configured to communicate using anyof these network protocols or technologies.

Additionally, one or more application programs 419 may be used by theparameter data system 400 (e.g., process software applications, deviceconfiguration software applications, control software applications, andthe like), including computer executable instructions for receiving andstoring data from refinery-based systems, and/or mobile computingdevices, determining and configuring the mobile computing device basedon the retrieved and analyzed data, and/or performing other relatedfunctions as described herein.

The processor 403 may be configured to issue or recommend a commandmessage to adjust conditions in reactor 30. The command message may betransmitted from the parameter data system 400 in an encrypted orunencrypted message that commands one or more adjustments to conditionsin reactor 30. The command may be communicated through the I/O module409, the modem 427 or the LAN interface 423 through thesecurity/integration layer 460 and received by a network device 435 orterminals 441, 451 in reactor 30 or the refinery comprising reactor 30to cause adjustments or halting/starting of one or more operations inthe reactor 30 or the refinery. The command message may be transmittedto a terminal 441, 451 for processing and/or execution. In analternative embodiment, the command may be directly communicated, eitherwirelessly or in a wired fashion, to physical components in reactor 30or in the refinery containing reactor 30 such that the physicalcomponents include a network device 435 to receive the commands andexecute the command. Terminals 441, 451 may automatically signalexecution of the command or a prompt to an operator to manually executethe adjustment. Such adjustment command messages can be transmitted backto reactor 30 to be received and executed to modify or improveperformance of reactor 30.

Without further elaboration, it is believed that using the precedingdescription that one skilled in the art can utilize the presentinvention to its fullest extent and easily ascertain the essentialcharacteristics of this invention, without departing from the spirit andscope thereof, to make various changes and modifications of theinvention and to adapt it to various usages and conditions. Thepreceding preferred specific embodiments are, therefore, to be construedas merely illustrative, and not limiting the remainder of the disclosurein any way whatsoever, and that it is intended to cover variousmodifications and equivalent arrangements included within the scope ofthe appended claims. In the foregoing, all temperatures are set forth indegrees Celsius and, all parts and percentages are by weight, unlessotherwise indicated.

It should be appreciated and understood by those of ordinary skill inthe art that various other components, such as valves, pumps, filters,coolers, etc., were not shown in the drawings as it is believed that thespecifics of same are well within the knowledge of those of ordinaryskill in the art and a description of same is not necessary forpracticing or understanding the embodiments of the present invention.

While at least one exemplary embodiment has been presented in theforegoing detailed description of the invention, it should beappreciated that a vast number of variations exist. It should also beappreciated that the exemplary embodiment or exemplary embodiments areonly examples, and are not intended to limit the scope, applicability,or configuration of the invention in any way. Rather, the foregoingdetailed description will provide those skilled in the art with aconvenient road map for implementing an exemplary embodiment of theinvention. It being understood that various changes may be made in thefunction and arrangement of elements described in an exemplaryembodiment without departing from the scope of the invention as setforth in the appended claims.

Examples are provided below so that the invention may be described morecompletely. These examples are only by way of illustration and shouldnot be interpreted as a limitation of the broad scope of the invention,which is set forth in the claims.

Patterns presented in the following examples were obtained usingstandard x-ray powder diffraction techniques. The radiation source was ahigh-intensity, x-ray tube operated at 45 kV and 35 mA. The diffractionpattern from the copper K-alpha radiation was obtained by appropriatecomputer based techniques. Powder samples were pressed flat into a plateand continuously scanned from 3° and 70° (2θ). Interplanar spacings (d)in Angstrom units were obtained from the position of the diffractionpeaks expressed as θ, where θ is the Bragg angle as observed fromdigitized data. Intensities were determined from the integrated area ofdiffraction peaks after subtracting background, “I_(O)” being theintensity of the strongest line or peak, and “I” being the intensity ofeach of the other peaks. As will be understood by those skilled in theart the determination of the parameter 2θ is subject to both human andmechanical error, which in combination can impose an uncertainty ofabout ±0.4° on each reported value of 2θ. This uncertainty is alsotranslated to the reported values of the d-spacings, which arecalculated from the 2θ values. In some of the x-ray patterns reported,the relative intensities of the d-spacings are indicated by thenotations vs, s, m, and w, which represent very strong, strong, medium,and weak, respectively. In terms of 100(I/I₀), the above designationsare defined as:

-   -   w=0.01-15, m=15-60: s=60-80 and vs=80-100.

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present. As willbe understood to those skilled in the art, it is possible for differentpoorly crystalline materials to yield peaks at the same position. If amaterial is composed of multiple poorly crystalline materials, then thepeak positions observed individually for each poorly crystallinematerial would be observed in the resulting summed diffraction pattern.Likewise, it is possible to have some peaks appear at the same positionswithin different, single phase, crystalline materials, which may besimply a reflection of a similar distance within the materials and notthat the materials possess the same structure.

Example 1

Ammonium metatungstate hydrate (17.71 g, 0.07 moles of W) and ammoniumheptamolybdate tetrahydrate (5.3 g, 0.03 moles of Mo) were dissolved in150 ml of DI H₂O, concentrated ammonium hydroxide (25 mL, 30%) was addedto this solution. A second solution was prepared by adding nickelnitrate hexahydrate (43.62 g, 0.15 moles of Ni) to 150 ml of DI H₂O. Thetwo solutions were slowly mixed together over with the pH of the finalsolution being adjusted to pH 6.8 using a mild HNO₃ solution. Theprecipitated generated was isolated by filtration, washed with hot waterand then heat treated for using a ramp rate of 2° C. per hour until thetemperature reach 400° C. The material was kept at 300° C. for 24 hours.The resulting product was analyzed by X-ray powder diffraction, and theX-ray powder diffraction pattern is shown in the Figure.

Example 2

Using a ceramic dish, ammonium hydroxide (10 ml, 30%) was added tonickel carbonate hydrate (10.14 g, 0.1 moles of Ni) over a 30 minuteperiod. Ammonium metatungstate hydrate (17.71 g, 0.07 moles of W) andammonium heptamolybdate tetrahydrate (1.76 g 0.01 moles of Mo) wereadded and the resultant mixture was mixed thoroughly and then heattreated for 12 hours at 150° C. with intermittent mixing. The mixturewas then heat treated further at 350° C. for 24 hours. The resultingproduct was analyzed by X-ray powder diffraction, and the X-ray powderdiffraction pattern is shown in the Figure.

Example 3

Using a ceramic dish, nickel nitrate hexahydrate (14.54 g, 0.05 moles ofNi), zinc nitrate hexahydrate (14.87 g, 0.05 moles of Zn), ammoniummetatungstate hydrate (17.71 g, 0.07 moles of W) and ammoniumheptamolybdate tetrahydrate (1.76 g 0.01 moles of Mo) were addedtogether and the resultant mixture was mixed thoroughly before beingheat treated for 12 hours at 150° C. with intermittent mixing. Themixture was then heat treated further at 350° C. for 24 hours. Theresulting product was analyzed by X-ray powder diffraction, and theX-ray powder diffraction pattern is shown in the Figure.

Example 4

Using a ceramic dish, nickel nitrate hexahydrate (29.75 g, 0.1 moles ofNi) and ammonium metatungstate hydrate (17.71 g, 0.07 moles of W) andammonium heptamolybdate tetrahydrate (7.06 g 0.04 moles of Mo) wereadded together and the resultant mixture was mixed thoroughly beforebeing heat treated for 12 hours at 150° C. with intermittent mixing. Themixture was then heat treated further at 300° C. for 24 hours. Theresulting product was analyzed by X-ray powder diffraction, and theX-ray powder diffraction pattern is shown in the Figure.

Example 5

Nickel nitrate hexahydrate (100 g, 0.34 moles of Ni), zinc nitrate (3.63g, 0.03 moles of Zn), ammonium metatungstate hydrate (60.5 g, 0.24 molesof W), ammonium heptamolybdate tetrahydrate (1.76 g 0.01 moles of Mo)and ammonium carbonate (82.5 g, 0.86 moles) were mixed together in acovered beaker and heated at 50° C. for 4 days with intermittent mixing.The mixture was then transferred to a ceramic dish and was heated at 70°C. for 1 day, before being heated to 120° C. The mixture was then heatedfor 1 hour at 10° C. intervals from 120° C. to 190° C., after which thematerial was heated at 200° C. for 24 hrs. The resulting product wasanalyzed by X-ray powder diffraction, and the X-ray powder diffractionpattern is shown in the Figure.

Specific Embodiments

Embodiment 1 is a crystalline transition metal molybdotungstate materialhaving the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from0.5 to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from0.01 to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sumof the valency of M, x and y; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

Another embodiment is the crystalline transition metal molybdotungstatematerial of embodiment 1 wherein the crystalline transition metalmolybdotungstate material is present in a mixture with at least onebinder and wherein the mixture comprises up to 25 wt-% binder.

Another embodiment is any of the previous crystalline transition metalmolybdotungstate materials wherein the binder is selected from the groupconsisting of silicas, aluminas, silica-aluminas, and mixtures thereof.

Another embodiment is any of the previous crystalline transition metalmolybdotungstate materials wherein M is nickel or cobalt.

Another embodiment is any of the previous crystalline transition metalmolybdotungstate materials wherein M is nickel.

Another embodiment is any of the previous crystalline transition metalmolybdotungstate materials wherein the crystalline transition metalmolybdotungstate material is sulfided.

Embodiment 2 is a method of making a crystalline transition metalmolybdotungstate material having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4 to 2.5, or from0.5 to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from0.01 to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sumof the valency of M, x and y; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 mthe method comprising: (a) forming a reaction mixture containing water,a source of M, a source of Mo, a source of W, and optionally asolubilizing agent, complexing agent, chelating agent, or a mixturethereof; (b) optionally removing a component from the reaction mixtureto generate an intermediate reaction mixture wherein the component is aprecipitate, or at least a portion of the water, or both a precipitateand a portion of the water; (c) reacting the reaction mixture or theintermediate mixture at a temperature from about 25° C. to about 500° C.for a period of time from about 30 minutes to 14 days to generate thecrystalline transition metal molybdotungstate material; and (d)recovering the crystalline transition metal molybdotungstate material.

Another embodiment is the method of embodiment 2 wherein the recoveringis by filtration or centrifugation.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material furthercomprising adding a binder to the recovered crystalline transition metalmolybdotungstate material.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material wherein thebinder is selected from the group consisting of aluminas, silicas,alumina-silicas, and mixtures thereof.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material furthercomprising sulfiding the recovered crystalline transition metalmolybdotungstate material.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material wherein thereacting is conducted under atmospheric pressure or autogenous pressure.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material furthercomprising intermittent mixing during the reacting.

Another embodiment is any of the previous methods method of making thecrystalline transition metal molybdotungstate material wherein thetemperature is varied during the reacting.

Embodiment 3 is a conversion process comprising contacting a materialwith a sulfiding agent to convert at least a portion of the material tometal sulfides and contacting the metal sulfides with a feed atconversion conditions to generate at least one product, wherein thematerial comprises a crystalline transition metal molybdotungstatematerial having the formula:

MMo_(x)W_(y)O_(z)

where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V, Cu, Zn, Sn, Sb,Ti, Zr, and mixtures thereof ‘x+y’ varies between 0.4 to 2.5, or from0.5 to 1.5, or from 0.6 to 1; ‘x’ varies from 0.0001 to 0.75, or from0.01 to 0.6, or from 0.1 to 0.4; ‘z’ is a number which satisfies the sumof the valency of M, x and y; the material is further characterized by ax-ray powder diffraction pattern showing peaks at the d-spacings listedin Table A:

TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs 2.41 s 2.33 s 2.09vs 1.93 m

Another embodiment is embodiment 3 wherein the conversion process ishydroprocessing.

Another embodiment is wherein the conversion process is selected fromthe group consisting of hydrodenitrification, hydrodesulfurization,hydrodemetallation, hydrodesilication, hydrodearomatization,hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

Another embodiment is any of the previous conversion processes whereinthe crystalline transition metal molybdotungstate material is present ina mixture with at least one binder and wherein the mixture comprises upto about 25 wt-% binder.

Another embodiment is any of the previous conversion processes whereinthe crystalline transition metal molybdotungstate material is sulfided.

Another embodiment is embodiment 2 or 3 further comprising at least oneof: sensing at least one parameter of the process or method andgenerating a signal or data from the sensing; or generating andtransmitting a signal; or generating and transmitting data.

1. A conversion process data system comprising: (a) at least oneprocessor; (b) at least one memory storing computer-executableinstructions; and (c) at least one receiver configured to receive dataof a conversion process comprising at least one reaction catalyzed by atleast one metal sulfide resulting from the decomposition by sulfidationof a material comprising a crystalline transition metal molybdotungstatematerial having the formula:MMo_(x)W_(y)O_(z) where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V,Cu, Zn, Sn, Sb, Ti, Zr, and mixtures thereof ‘x+y’ varies between 0.4 to2.5; ‘x’ varies from 0.0001 to 0.75; ‘z’ is a number which satisfies thesum of the valency of M, x and y; the material is further characterizedby a x-ray powder diffraction pattern showing peaks at the d-spacingslisted in Table A: TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs2.41 s 2.33 s 2.09 vs 1.93 m


2. The system of claim 1 further comprising an Input/Output device tocollect the data, or evaluate the date, or correlate the data, or anycombination thereof.
 3. The system of claim 1 further comprising atransmitter to transmit a signal to the conversion process.
 4. Thesystem of claim 3 wherein the signal comprises instructions.
 5. Thesystem of claim 4 wherein the signal comprises instructions regarding anadjustment to a parameter.
 6. The system of claim 1 further comprisingcollecting data from multiple systems wherein one system is theparameter data system.
 7. The system of claim 1 wherein the processor isconfigured to generate predictive information or quantitativeinformation.
 8. A method-of-making data system comprising: (a) at leastone processor; (b) at least one memory storing computer-executableinstructions; and (c) at least one receiver configured to receive dataof a method of making a crystalline transition metal molybdotungstatematerial having the formula:MMo_(x)W_(y)O_(z) where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V,Cu, Zn, Sn, Sb, Ti, Zr, and mixtures thereof; ‘x+y’ varies between 0.4to 2.5; ‘x’ varies from 0.0001 to 0.75; ‘z’ is a number which satisfiesthe sum of the valency of M, x and y; the material is furthercharacterized by a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A: TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12vs 2.74 vs 2.41 s 2.33 s 2.09 vs 1.93 m

the method comprising: (a) forming a reaction mixture containing water,source of M, source of W, source of Mo, and optionally a solubilizingagent, complexing agent, chelating agent, or a mixture thereof; (b)optionally removing a component from the reaction mixture to generate anintermediate reaction mixture wherein the component is a precipitate, orat least a portion of the water, or both a precipitate and at least aportion of the water; (c) reacting the reaction mixture or theintermediate mixture at a temperature from about 25° C. to about 500° C.for a period of time from about 30 minutes to 14 days to generate thecrystalline transition metal molybdotungstate material; and (d)recovering the crystalline transition metal molybdotungstate material.9. The system of claim 8 further comprising an Input/Output device tocollect the data, or evaluate the date, or correlate the data, or anycombination thereof.
 10. The system of claim 8 further comprising atransmitter to transmit a signal to the conversion process.
 11. Thesystem of claim 10 wherein the signal comprises instructions.
 12. Thesystem of claim 10 wherein the signal comprises instructions regardingan adjustment to a parameter.
 13. The system of claim 8 furthercomprising collecting data from multiple systems wherein one system isthe parameter data system.
 14. The system of claim 8 wherein theprocessor is configured to generate predictive information orquantitative information.
 15. A method for collecting data from aconversion process, the method comprising receiving data from at leastone sensor of a conversion process, the conversion process comprising atleast one reaction catalyzed by at least one metal sulfide derived fromthe decomposition by sulfidation of a crystalline transition metalmolybdotungstate material having the formula:MMo_(x)W_(y)O_(z) where ‘M’ is a metal selected from Mn, Fe, Co, Ni, V,Cu, Zn, Sn, Sb, Ti, Zr, and mixtures thereof ‘x+y’ varies between 0.4 to2.5; ‘x’ varies from 0.0001 to 0.75; ‘z’ is a number which satisfies thesum of the valency of M, x and y; the material is further characterizedby a x-ray powder diffraction pattern showing peaks at the d-spacingslisted in Table A: TABLE A d(Å) I/I0 (%) 6.20 s 3.52 vs 3.12 vs 2.74 vs2.41 s 2.33 s 2.09 vs 1.93 m


16. The method of claim 15 wherein the conversion process ishydroprocessing.
 17. The method of claim 15 wherein the conversionprocess is hydrodenitrification, or hydrodesulfurization, orhydrodemetallation, or hydrodesilication, or hydrodearomatization, orhydroisomerization, or hydrotreating, or hydrofining, or hydrocracking.18. The method of claim 15 further comprising at least one of displayingor transmitting or analyzing the received data.
 19. The method of claim15 further comprising analyzing the received data to generate at leastone instruction and transmitting the at least one instruction.
 20. Themethod of claim 15 further comprising analyzing the received data andgenerating predictive information or quantitative information.